Lubricating oils containing high molecular weight mannich condensation products

ABSTRACT

OIL SOLUBLE HIGH MOLECULAR WEIGHT MANNICH CONDENSATION PRODUCTS FORMED BY REACTING (1) HIGH MOLECULAR WEIGHT ALKYL-SUBSTITUTED HYDROXY AROMATIC COMPOUNDS WHOSE ALKYL-SUBSTITUENT HAS A NUMBER AVERAGE MOLECULAR WEIGHT (MN) FROM ABOUT 600-1000,000, (2) A COMPOUND CONTAINING AT LEAST HN&lt; GROUP, AND (3) AN ALDEHYDE IN THE RESPECTIVE MOLAR REACTANT RATIO OF 1:0.1-10:1.0-10, ARE HIGHLY EFFICIENT ASHLESS TYPE (METAL FREE) DISPERSANTDETERGENT LUBRICANT OIL ADDITION AGENTS. LUBRICATING OILS CONTAINING THESE COMPOSTIONS PROVIDE A HIGH DEGREE OF PROTECTION AGAINST THE DEPOSITION OF SLUDGE AND VARNISH AND CORROSION WHERE USED AS CRANKCASE LUBRICANTS. BISMANNICH PRODUCTS PREPARED BY CONDENSING (1) A 8502500 MN POLYALKYL-SUBSTITUTED PHENOL, (2) AN ALKYLENE POLYAMINE AND (3) FORMALDEHYDE IN THE RESPECTIVE MOLAR RATIO OF 2.0:1.5-2.1 ARE NOVEL PRODUCTS AND ARE ESPECIALLY EFFECTIVE FOR HIGH SEVERITY DETERGENT-DISPERSANT FUNCTION OVER THE EXTENDED OIL DRAIN RANGE OF CRANKCASE LUBRICANT OILS RECOMMENDED BY AUTOMOBILE MANUFACTURES.

United States Patent LUBRICATING OILS CONTAINING HIGH MOLEC- ULAR WEIGHT MANNICH CONDENSATION PRODUCTS Edmund J. Piasek, Chicago, Ill., and Robert E. Karl],

Munstfii', Ind., assignors to Standard Oil Company, Chicago,

No Drawing. Continuation-impart of application Ser. No. 502,368, Oct. 22, 1965, now Patent No. 3,539,633. This application Feb. 10, 1969, Ser. No. 798,102

Int. Cl. Cm 1/20, 1/32 U.S. Cl. 252-515 R 6 Claims ABSTRACT OF THE DISCLOSURE Oil soluble high molecular weight Mannich condensation products formed by reacting (1) high molecular weight alkyl-substituted hydroxy aromatic compounds whose alkyl-substituent has a number average molecular weight (Mn) from about 600100,000, (2) a compound containing at least HN group, and (3) an aldehyde in the respective molar reactant ratio of 1:0.110:1.0-10, are highly efiicient ashless type (metal free) dispersantdetergent lubricant oil addition agents. Lubricating oils containing these compositions provide a high degree of protection against the deposition of sludge and varnish and corrosion when used as crankcase lubricants. Bis- Mannich products prepared by condensing (1) a 850- 2500 En polyalkyl-substituted phenol, (2) an alkylene polyamine and (3) formaldehyde in the respective molar ratio of 1.0:0.71.0:1.52.1 are novel products and are especially effective for high severity detergent-dispersant function over the extended oil drain range of crankcase lubricant oils recommended by automobile manufacturers.

RELATED APPLICATIONS This application is a continuation-in-part of our copending application Ser. No. 502,368, filed Oct. 22, 1965, now U.S. Pat. No. 3,539,633.

BACKGROUND OF THE INVENTION This invention relates to improved lubricating oils and particularly concerns automobile and diesel crankcase lubricating oil formulations containing a minor amount of a new class of oil-soluble addition agents which improve the performance of the oil, particularly its dispersantdetergent function thus enabling lubricating oils to provide a high degree of protection of the lubricated parts of internal combustion engines.

Present-day automobile and diesel engines have been designed for higher power output, lower combustion products emission and longer in-service periods of use of crankcase lubricating oils. These design changes have resulted in such severe operating conditions as to necessitate devising higher efficiency lubricating oils that will, under the increased severity of in-service use, afford proper protection against corrosion and the accumulation or deposition of sludge, varnish and resinous materials on the surface of engine parts which rapidly accelerate decrease in both operating efficiency and life of the engine. The principal ingredient of crankcase lubricants is a base lubricating oil, a mixture of hydrocarbons derived from petroleum. Even when highly refined by removal of deleterious components, such as polymerizable components, acid formers, waxes, etc., a lubricant base oil still requires the addition of a number of oil-soluble chemical additives to enable the oil to resist oxidation, deposition of sludge and varnish on, and corrosion of, the lubricated metal parts, and to provide added lubricity and regulated viscosity change from low to high temf. we

perature. These ingredients are commonly known as antioxidants, dispersant-detergents, pour point dispersants, etc.

Combustion products from the burning of fuel and thermal degradation of lubricating oils and addition agents tend to concentrate in the crankcase oil with the attendant formation of oil-insoluble deposit-forming products, that either surface coat the engine parts (varnish or lacquerlike films) or settle out on the engine parts as viscous (sludge) deposits or for-m solid ash-like or carbonaceous deposits. Any of such deposits can restrict, and even plug, grooves, channels and holes provided for lubricant flow to the moving surfaces of the engine requiring lubrication thus accelerating the wear and thus reducing the efiiciency of the engine. In addition, acidic combustion products corrode the lubricated metal surfaces. Chemical additives are blended in crankcase oil formulations not only to reduce thermal decomposition of the oil and addition agents (anti-oxidants) but also to keep in suspension (as a dispersant) and to resuspend (as a detergent) insoluble combustion and degradation products as well as to neutralize acidic products (anti-corrosion agents). A separate additive is usually added for each improvement to be effected.

Various ingredients have been developed for the purpose of providing the dispersant-detergent function. Neutral and overbased metallo-organic compounds, such as the alkaline earth metal salts of sulfonic acids and hydrocarbon-P 5 reaction products were the first addition agents used for this purpose. Their in-service drawbacks included the formation of metal-ash thermal decomposition products which deposited on engine parts; they could not efiiciently disperse or resuspend lacquer or varnish formers or sludge formers; and they lost their dispersant-detergent function when their alkaline earth metal component had been consumed in neutralizing acidic products of combustion.

As performance levels increased and the recommended periods between oil drains lengthened for both automobile and railway Diesel engines, more efiicient dispersancy and detergency performance as well as acid neutralization and lower ash-forming tendency were demanded for lubricating oil formulations. During the past several years, a. great deal of time and effort has been directed at providing addition agents for lubricants capable of satisfying such performance demands. When high molecular weight polybutene polymers became commercially available in the early l940s, research workers in various laboratories devised, for this dispersant-detergent function, a series of derivatives of polybutene-phosphorus pentasulfide reaction products, e.g., alkaline earth metal salts, alkylene polyamine and alkylene oxide derivatives, in which the high molecular weight of the polybutene group greatly enhanced their effectiveness. Others devised amine salts, amides, imides and amidines of polybutenyl-substituted polycarboxylic acids and polymeric compounds having pendant or grafted-on polar groups. Still others suggested combinations of alkaline earth metal sulfonates and Mannich condensation products of a low molecular weight alkyl (C -C substituted hydroxyaromatic compound, an amine having at least one replaceable hydrogen on a nitrogen and an aldehyde and alkaline earth metal salts (phenates) of those Mannich condensation products but without notable success. The later compositions still possessed the objectionable feature of forming harmful metal-ash deposits, and were incapable of providing the increased dispersancy-detergency service demanded for long drain service of present-day engine requirements.

Mannich condensation products derived from alkylsubstituted hydroxyaromatic compounds having a relatively low molecular weight alkyl substituent, i.e., 2 to 20 carbon atoms in the alkyl substituent and chlorinated was (straight chain) type alkyl-substituents are described in US. Pat. Nos. 2,403,453; 2,353,491; 2,363,134; 2,459,- 112; 2,984,550 and 3,036,003. However, none of such prior Mannich condensation products are suitable for use as dispersant-detergent addition agents for presentday long drain oil interval in-service use.

One known type (US. Pat. No. 2,363,134) has been prepared by reacting, under Mannich reaction conditions, equimolar quantities of a C -C alkyl-substituted phenol and other hydroxy aromatic compounds, and N,N-di-substituted amine and formaldehyde according to the following equation:

wherein R is an alkyl group having between 2 and 20 carbon atoms and R and R may be alkyl, cycloalkyl, aryl or aralkyl radicals.

Other :prior low molecular weight Mannich condensation products formed by condensing a C to C alkylsubstituted phenol, an alkylene diamine and an aldehyde in the respective molar ratios of 2:1:2, have been illustrated by the following structural formula:

wherein R is a divalent alkylene hydrocarbon radical and R is an alkyl group containing from 2 to 20 carbon atoms.

Still others have been prepared by reacting C -C alkylphenols, formaldehyde and alkylene polyamines of the formula HzN-(A-N) wherein A is a divalent alkylene radical of 2 to 6 carbon atoms and n is an integer from 1 to 10, in the ratio of from 0.5 to 2 moles each of C -C alkylphenol and formaldehyde for each nitrogen group contained in the alkylene polyamine reagent. The molar reactant ratio range of (D -C alkylphenol, amine and formaldehyde used to form such products is 120:1.0:120. US. Pat. No. 3,036,003 exemplifies such products, which usually are formed with ethylene polyamines, according to the above formula in which A is -CH CH and N is 2, 3 and 4. For exampe, reaction of p-tertiary octylphenol, diethylene triamine, and formaldehyde in the respective molar ratios of 3:1:3 is illustrated by said patent as N N N -tri(Z-hydroxy-5-t-octylbenzyl) di-ethylene triamine and the reaction of the aforesaid reactants in the respective molar ratios of 2:1:2 is illustrated as being either N N, or N N -di-(2-hydroxy-5-t-octylbenzyl) diethylene triamine.

The foregoing prior C -C alkyl-substituted Mannich condensation products commonly are prepared by the conventional technique of adding the aliphatic aldehyde to a heated mixture of the alkylhydroxyaromatic and amine reagents, in the presence or absence of a solvent, and then heating the resultant mixture to a temperature between 100350 F. until dehydration is complete. A solvent such as benzene, toluene, xylene, methanol and others easily separated from the reaction mixture are light mineral oils, such as those used in blending stocks to prepare lubricating oil formulations in which the product is formed as a mineral oil concentrate are usually used. The water by-product is removed by heating the reaction mixture to a temperature suflicie y g least during the last part of the process, to drive off the water alone, or as an azeotropic mixture with the aromatic solvent, usually by the aid of an inert stripping gas such as nitrogen, carbon dioxide, etc.

The exactly neutralized or overbased alkaline earth metal salts (alkaline earth metal phenates) of those prior low molecular 'weight Mannich condensation products have been suggested for use in providing lubricating oils with a combination of detergent-inhibitor properties in one addition agent. The exactly neutralized alkaline earth metal salts have one equivalent of alkaline earth metal for each hydroxy group present. The overbased salts have, for each hydroxy group present, more than one equivalent of alkaline earth metal in the form of a hydroxy metaloxy, alkoxy metaloxy and even alkaline earth metal carbonate complex with hydroxy metaloxy on each benzene group as a replacement for the phenol hydroxy group. As noted above, said addition agent form objectionable metal ash deposits and have other performance deficiencies.

Certain hydroxy C C alkylbenzyl substituted ethylene polyamines have been suggested, in US. Pat. No. 3,036,003, as being useful per se in lubricating oil formulations as ashless-type detergents. The product resulting from the reaction of p-tertiary-octylphenol, tetraethylene pentamine and formaldehyde in a molar reactant ratio of 4:1:4, characterized as the tetra-(hydroxy-S-tertiaryoctylbenzyl) derivative of tetraethylene pentamine is indicated, by said patent, as capable of imparting detergency t-o lubricating oils on the basis of a carbon black suspension test described in the patent. However, that patent itself demonstrates, by an oxidation stability test, that the very same product is a lubricating oil formulation, with no other detergent added, permits sludge and varnish formation as well as oxidation of the base oil. Thus, US. Pat. No. 3,036,003 demonstrates that its Mannich condensation products, when added as the sole detergent agent in a lubricatingoil, are incapable of providing a satisfactory level of detergency and are also incapable of inhibiting oxidation of the base oil.

US. Pat. No. 3,235,484 issued Feb. 15, 1966 (now Reissue No. 26,330) describes the addition agents of certain disclosed compositions to refinery hydrocarbon feed stocks for the purpose of inhibiting the accumulation of carbonaceous deposits in refinery cracking units. The primary inhibitors disclosed are mixtures of amides, imides and amine salt formed by reacting an ethylene polyamine with hydrocarbon substituted succinic acids or anhydrides, whose hydrocarbon substituent has at least about 50 carbon atoms. As an adjunct for such primary carbonaceous deposit inhibitors there is disclosed in said patent Mannich condensation products formed by reacting 1) alkylphenol, (2) an amine and (3) formaldehyde in the ratio of one mole alkylphenol and from 0.1-10 mole formaldehyde for each active nitrogen group contained in the amine reactant. Alkylphenols whose alkyl group has a molecular weight as high as 50,000 and contains from monoalkylphenols whose alkyl group contains 4-30 carbon atoms are stated to be the preferred alkylphenol reactants.

BRIEF SUMMARY OF THE INVENTION This invention pertains to improved lubricating oils and is predicated upon the discovery of a new class of multifunctional addition agents for lubricating oils, particularly those used in internal combustion engines in which they function as highly efficient dispersant-detergent and also act as inhibitors of oxidation.

The new class of compounds which are employed as additives according to our invention are oil-soluble high molecular weight Mannich condensation products. They may be prepared in the usual manner by cendensing under Mannich reaction conditions:

( 1) An alkyl-substituted hydroxyaromatic compound,

whose alkyl-substituent has a 600100,000 fin, prefere ably a polyalkylphenol whose polyalkyl substituent is derived from l-mono-olefin polymers having a fin of about 850-2500;

(2) An amine containing at least one NH group, preferably an alkylene polyamine of the formula NHz A-N H t). wherein A is a divalent alkylene radical having 2 to 6 carbon atoms and x is an integer from 1 to and (3) An aldehyde, preferably formaldehyde.

In general, the foregoing high molecular weight Mannich condensation products of this invention are prepared according to the conventional methods heretofore employed for the preparation of low molecular weight Mannich condensation products, using the above-named reactants in the respective molar ratios of high molecular weight alkyl-substituted hydroxyaromatic compound, amine and aldehyde of approximately 1:0.1-l0:1.0-10. They may conveniently be prepared by the usual Mannich condensation procedure which involves adding the formaldehyde reagent (e.g., formalin) to a mixture of reagent (1) and (2) above or in an easily removed organic solvent, such as benzene, xylene or toluene or in solvent refined neutral oil and then heating the reaction at an elevated temperature (IOU-350 F.) until dehydration is complete.

The preferred additives according to this invention are high molecular weight bis-Mannich condensation products formed by reacting (1) a 850-2500 fin polyalkylphenol; (2) an ethylene polyamine, bis-carbazmide or bisthiocarbamide as amine reactant; and (3) formaldehyde in the respective molar ratio of 1.0:0.7-1.0:1.5-2.1. These can be prepared by the general method or by a two-step condensation method in which the formaldehyde is added in two reaction stages in lieu of adding all of the formaldehyde to reactants (l) and (2) as in the general procedure. For example, when the two-step precedure is employed using a respective reactant molar ratio of 1.0:0.7:1.5, all of the alkylphenol and amine reactant and about twothirds of the formaldehyde are heated, usually in a solvent such as mineral oil, at approximately 130-300 F. until dehydration is complete to form an inter-mediate Mannich condensation product. Thereafter the remaining portion of formaldehyde is added, usually at ISO-300 F., and the resulting fixture heated and maintained at approximately 250-350 F. from 1 to 5 hours until dehydration is complete to form the final product.

With equimolar amounts of all reactants, the theoretical first-stage intermediate product is a 1:1:1 condensation product. Infrared analysis of this intermediate indicates, by the strong 12.1 micron band representing the unsubstituted 5 and 6 ring positions, the presence of a single CH group on the benzene ring in the position ortho to the hydroxy group substituent. On the basis of infrared data, the predominant first-step product formed using a high molecular weight alkylphenol, formaldehyde and an alkylene polyamine, bis-carbamide or bis-thiocarbamide, may be postulated as having the following structure:

wherein R is an alkyl radical containing from 50 to 20,000 carbon atoms and Y is H(IIIA) or (H(N-A f H x H 2 Z wherein A is a saturated alkylene radical having from 2 to 6 carbon atoms, X is an integer from 1 to 10 and Z is '6 oxygen or sulfur. The latter are prepared from bis-carbarnides and bis-thiocarbamides of polyalkylene polyamines by reacting 2 moles of polyalkylene polyamine with 1 mole of urea or thiourea, respectively, accompanied by liberation of 2 moles of ammonia.

The second-stage product formed by reaction of the first-step intermediate with an additional mole of formaldehyde also exhibits a strong 12.1 micron infrared band. This would tend to exclude the formation of products having a methylene bridge linking 2 moles of the first-step intermediate to 5 and/or 6 ring position carbons in each mole. It appears probable that the formaldehyde used in the second step reacts with at least one of the terminal primary amino groups to form a NHCH OH terminal group as an intermediate which can thus react with a hydrogen of other terminal primary amino group or with the hydrogen on a 6 position carbon (the OH group retains its ortho directing character). In either type of condensation, water is formed as a by-product. When the second formaldehyde reaction step involves a condensation of the formaldehyde and hydrogen of both terminal primary amino groups, such a product can be called a tail-to-tail product. When the formaldehyde of the second reaction step reacts with one hydrogen of one terminal primary amino group to provide an N-(hydroxy methyl) substituent which, in turn, reacts with a 6 hydrogen splitting out water as a by-product, the final product can be called a tail-to-head product.

On this basis, the foregoing bis-Mannich reaction products may be postulated as containing compounds having the following structural formulas:

Tail-toTail wherein A, x and Z are as hereinbefore defined.

The above-described two-step process and general Mannich condensation preparative technique of adding all of the aldehyde reagent to a mixture of the high molecular weight hydroxyaromatic compound and an alkylene polyamine or bis-carbamide and the heating the mixture until dehydration is complete, produced, from the respective molar ratios of these reactants of 1:0.71:1.52.l produts substantially in nitrogen utilization, viscosity and inservice performance as dispersant-detergent addition agents.

The novel addition agents according to our invention are the high molecular weight Mannich condensation products of (1) high molecular weight alkyl substituted phenol whose alkyl substituent has a Mn of 600100,000, a compound having at least one HN group and an aldehyde wherein the respective molar ratio of the reactants is 1:0.110:l.010. Preferred addition agents are those obtained by condensing (1) an alkylphenol whose alkyl substituent is derived from l-mono-olefin polymers having a 8504500 Mn; (2) an alkylene polyamine having the formula H N(ANH),,H or a bis-(polyaminoalkyl) urea having the formula wherein A is a divalent saturated hydrocarbon radical having 2 to 6 carbon atoms and n is an integer from 1 to 10, and (3) a formaldehyde yield reactant used in the respective molar ratio of reactants is 1:0.7- 1.0:l.52.l.

The high molecular weight Mannich condensation products of this invention are exceptionally useful addition agents for lubricating oils imparting thereto dispersantdetergent and anti-oxidant properties at relatively low concentrations of the addition agent, e.g., 0.05 to 10 weight percent in formulated crankcase lubricating oil. Higher concentrations, e.g., 10 to 70 weight percent, are useful concentrates of the preparation of those formulated crankcase lubricating oils and the fortification of crankcase oil in use prior to the scheduled complete drain. In contrast, Mannich condensation products formed using low molecular weight alkyl substituted hydroxyaromatic compounds whose alkyl group contains 2 to 20 carbon atoms are unacceptable as dispersant-detergent addition agents for crankcase lubricating oils.

The foregoing superiority of the high molecular weight Mannich condensation products of this invention over the low molecular weight Mannich condensation products of the prior art is amply demonstrated by a comparison of their respective abilities to prevent sludge and varnish deposition in standardized industry accepted engine tests. One of the prerequisites for acceptance as a dispersantdetergent agent for in-service use in lubricating oils for present-day engines is the ability of addition agent to effectively provide, in those tests, a lubricating oil having a highly efiicient dispersancy-detergency function, which function is rated at the end of the engine tests, by visual inspection of the disassembled engine parts for sludge and varnish deposits. The results of the tests are scored on a 0-50 scale, a reading of 50 representing a clean engine free from detectable sludge and varnish. To be acceptable as a dispersant-detergent addition agent, a candidate must score on overall sludge and varnish deposit rating of 40 and over.

Low molecular weight C -C alkyl-substituted Mannich condensation products when used in crankcase lubricating oils as the sole source of dispersant-detergent addition agent at maximum concentration levels at which they can be incorporated in lubricating oil are unable to provide acceptable sludge or varnish ratings when evaluated in such standardized engine tests. On the other hand, the high molecular weight Mannich condensation products of this invention used as the sole dispersant-detergent addition agents in lubricating oils in tlhe range of 0.05-10, preferably 0.5-5.0, weight percent, provide crankcase lubricating oils which, when evaluated by the same standardized engine tests, scored sludge and varnish ratings of 40 and higher, even as high as 45 to 49.5.

EMBODIMENTS OF THE INVENTION Representative high molecular weight Mannich condensation products contemplated by this invention can be prepared by the following representative reactants of the classes before defined.

(1) High molecular weight alkyl-substituted hydroxyaromatics Representative of these high molecular weight alkylsubstituted hydroxyaromatic compounds are polypropylphenols may be obtained by the alkylation, in the presence of an alkylating catalyst, such as BF of phenol with high molecular weight polypropylene, polybutylene and other polyalkylene compounds to give alkyl substituents on the benzene ring of phenol having an average 600'- 100,000 fin. Their preparations using a BF phenol catalyst is described and claimed in our copending application Ser. No. 484,758, filed Sept. 2, 1965.

The 600 lTfn and high Mn alkyl-substituents on the hydroxyaromatic compounds may be derived from high molecular weight polypropylenes, polybutenes and other polymers of mono-olefins, principally l-mono olefins. Also useful are copolymers of mono-olefins with monomers copolymerizable therewith wherein the copolymer molecule contains at least by weight, of mono-olefin units. Specific examples are copolymers of butenes (butene-1, butene-2 and isobutylene) with monomers copolymerizable therewith wherein the copolymer molecule contains at least 90%, by weight, of propylene and butene units, respectively. Said monomers copolymerizable with propylene or said butenes include monomers containing a small proportion of unreactive polar groups such as chloro, bromo, keto, ethereal, aldehyde, which do appreciably lower the oil-solubility of the polymer. The comonomers polymerized with propylene or said butenes may be aliphatic and can also contain non-aliphatic groups, e.g., styrene, methyl styrene, p-dimethyl styrene, divinyl benzene and the like. From the foregoing limitation placed on the monomer copolymerized with propylene or said butenes, it is abundantly clear that said polymers and copolymers of propylene and said butenes are substantially aliphatic hydrocarbon polymers. Thus, the resulting alkylated phenol contain substantially alkyl hydrocarbon substituents having Mn upward from 600'.

In addition to these high molecular weight hydroxyaromatic compounds others which may be used include those which have been used to prepare prior low molecular weight Mannich condensation products, e.g., high molecular weight alkyl-substituted derivatives of resorcinol, hydroquinone, cresol, catechol, xylenol, hydroxy diphenyl, benzylphenol, phenethylphenol, naphthol, tolylnaphthol, among other. Preferred for the preparation of the before mentioned preferred bis Mannich condensation products are the polyalkylphenol reactants, e.g., polypropylphenol and polybutylphenol whose alkyl group has an average number molecular weight of 600-3000 and polypropylphenol whose alkyl group has an average molecular weight of 750-1200 and, the most preferred being polybutylphenol whose alkyl group has an average number molecular weight of 850-2500.

(2) HN group containing reactants Representative of this class of reactants are alkylene polyamines, principally polyethylene polyamines. Other representative organic compounds containing at least one HN group suitable for use in the preparation of Mannich condensation products are well known and include polyalkylpolyamines, the mono and di-amino alkanes and their substituted analogs, e.g., ethylamine and diethanol amine; aromatic diamines, e.g., phenylene diamine, diamino naphthalenes; heterocyclic amines, e.g., morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine; melamine and their substituted analogs.

Suitable alkylene polyamine reactants include ethylenediamine, diethylene triarnine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene hepta-amine, heptaethylene octamine, octaethylene nonamine, nonaethylene decamine and decaethylene undecamine and mixture of such amines having nitrogen contents corresponding to the alkylene polyamines, in the formula H N-(ANH),,H, mentioned before, A is divalent ethylene and n is 1 to of the foregoing formula. Corresponding propylene polyamines such as propylene diamine and di-, tri-, tetra-, penta-propylene tri-, tetra-, pentaand heXa-amines are also suitable reactants. The alkylene polyamines are usually obtained by the reaction of ammonia and dihalo alkanes, such as dichloro alkanes. Thus the alkylene polyamines obtained from the reaction of 2 to 11 moles of ammonia with l to 10 moles of dichloro alkanes having 2 to 6 carbon atoms and the chlorines on different carbons are suitable alkylene polyamine reactants.

Also suitable are condensation products of urea or thiourea and the alkylene polyamines wherein for each X moles of urea or thiourea 2X moles of alkylene polyamine are used. Such a condensation product from two moles of alkylene polyamine and one mole of urea has the formula:

Aldehyde reactants Representative aldehyde reactants contemplated for use in the preparation of the high molecular weight Mannich condensation products of this invention include the aliphatic aldehydes such as formaldehyde (also as paraformaldehyde and formalin), acetaldehyde and aldol (bhydroxybutyraldehyde). We prefer to use formaldehyde or a formaldehyde yielding reactants.

The following examples will serve to illustrate specific embodiments of this invention prepared according to the well-known classical one-step Mannich condensation process.

Example 1 There are combined, stirred and heated to 320 F., 50 grams of SAE 5W weight oil, 100 grams (0.112 mole) of 892 Mn polypropyl (C substituted phenol and 5.24 ml. (0.0283 mole) tetraethylene pentamine. Thereafter 0.122 mole formaldehyde is added rapidly. Nitrogen is injected into the stirred mixture held at 300 F. for 90 minutes to remove by-product water. The dried solution is clear and has a red color. The solution contains 68.8% of high molecular weight (985 Min) Mannich condensation product of 1.8% nitrogen. The respective molar ratio of reactants substituted phenolzaminezaldehyde used is 1:0.25:1.09.

To demonstrate the dispersancy property of the high molecular weight Mannich condensation product of Example 1, there is dissolved 0.264 gram of the solution in 90 ml. of naphtha. To that naphtha solution there is added 4.0 grams of lamp black, the mixture is shaken and permitted to stand overnight (about 16 hours). After standing 16 hours the carbon black was still well dispersed in the naphtha solution of the solution of high molecular weight Mannich condensation product prepared according to Example 1.

10 Example 2 There are combined, stirred and heated to 200 F., 200 grams (0.222 mole) of polypropyl (C phenol of 900 Mn and 10.5 ml. (0.055 mole) tetraethylene pentamine. Thereafter 0.25 mole formaldehyde (20 ml. of formalin) is added all at one time. The mixture became frothy and viscous. After frothing subsided (upon cooling) the mixture is heated and injected with nitrogen until the product is substantially free of by-product water. This high molecular weight Mannich condensation product has a viscosity at 210 F. of 21,621 SSU, is soluble in lubricating oil and has a 2300 fin. The ratio of polypropylphenol: aminezaldehyde reactants used is in the molar ratio of l:0.247:1.l26.

Example 3 The method of Example 2 is repeated except 0.055 mole diethylene triamine is used in place of 0.055 mole tetraethylene pentamine. The resulting product is all high molecular Weight (2023 fin) Mannich condensation product, soluble in lubricating oil and has a viscosity of 16,340 SSU at 210 F. The ratio of polypropylphenol:amine:aldehyde reactants used is in the molar ratio of 1:0.247: 1.126. The product of this method is a clear liquid at 210 F.

Example 4 There are combined, stirred and heated to 180 F. a mixture of 200 grams (0.222 mole) of 900 fin polypropyl substituted phenol and 84 grams (0.444 mole) of tetraethylene pentamine. Thereafter 36 ml. of formalin solution (37% CH;,,()) to provide 0.444 mole of formaldehyde is added rapidly. The temperature of the reaction mixture increases during formalin addition. After adding formalin the stirred mixture is heated to 300 F. and held there for several hours and then held at reduced pressure under vacuum distillation conditions to remove by-product water. The dried product is all high molecular weight (994 fin) Mannich condensation product having a viscosity of 3386 SSU at 210 F. The ratio of phenol: amine:aldehyde used is in the molar ratio of 1:2:2.

Example 5 The preparative method of Example 4 is repeated using the same reactants except in the quantities of 0.222 mole of 900 Mn polypropyl substituted phenol, 0.111 mole tetraethylene pentamine and 0.222 mole of formaldehyde to provide the respective molar ratio of 110.5 :1. The resulting product is all high molecular weight Mannich condensation product (1892 Mn having a viscosity of 13,840 SSU at 210 F.

Example 6 There are combined, stirred and heated to 180 F., 0.222 mole of polypropyl substituted phenol (900 Mn) and 0.222 mole of diethanolamine. Thereafter 0.222 mole of formaldehyde is added and then the temperature of the stirred mixture is raised to 310 F. At that temperature nitrogen was injected into the stirred liquid to remove byproduct water. The respective molar ratio of phenol: aminezaldehyde used is 1:1:1. The dried liquid product is clear but upon cooling becomes a dark viscous liquid and has a molecular weight (1005 Mn) and a viscosity of 16,269 SSU at 210 F.

To ml. of naphtha there is added 0.1 gram of the product of Example 6 and 4 grams of lamp black in 16 grams of white oil. This mixture is shaken and permitted to stand 20 hours. After standing 20 hours the carbon black was still well dispersed.

Example 7 There are combined, stirred and heated to 200 F. 0.445

mole of polypropyl-substituted phenol (900 Mn) and 0.111 mole tetraethylene pentamine. Then 36 ml. formalin (37 CH O) is added to provide 0.445 mole formaldehyde. This mixture is quite viscous at 200 F. so to facilitate stirring the reaction product is heated to 300 F. and injected with nitrogen to remove by-product water. The dried product is al lhigh molecular weight (3800 Mn) Mannich condensation product. The ratio of phenol: aminezaldehyde used is in the respective molar ratio of 1:0.24911.

It is desirable to known the anti-corrosion protection to bearing metals afforded by detergent-dispersants. One test used is the Stirred Sand Corrosion Test. This test is conducted in an iron beaker to which are added 250 grams of solvent extracted SAE 30 weight oil, a tared copper-lead bearing, suspended in the oil, 50 grams of 3035 mesh (Tyler Screen Size Standard) sand, 0.625 gram lead oxide, 1.25 grams of a zinc dialkyl dithiophosphate oxidation inhibitor, and the detergent-dispersant detergent. The Cu-Pb bearing is lightly abraded with steel wool, washed with naptha, dried and weighed to the nearest milligram before suspending it in the oil. The beaker and its contents are kept at a constant temperature of 300 F. (:2 F.) while the contents are stirred at 750 rpm. in contact with air. Lead oxide is used to simulate blow-by of lead past piston rings from combustion of leaded fuels into the engine crankcase. At the end of the test the bearing is removed, washed with naphtha, dried and weighed to the nearest milligram. Acidity of the oil after the test is determined in milligrams KOH per gram sample of oil. Tests are run on duplicates, one for 48 hours and one for 72 hours. The results of these tests conducted with high molecular weight Mannich condensation products of this invention and a control bis-succinimide detergent-dispersant are set out in the following table.

STIRRED SAND CORROSION TEST RESULTS Bearing weight loss, Acidity, mg. Detergent-dispersant mg. K lgram Example Amount, 48 hrs. 72 hrs. 48 hrs. 72 hrs.

grams In the above table ND. indicates no determination for the test in question. The high molecular weight Mannich condensation products do, as the tabulated test data indicate, exert anti-corrosion properties to lubricating oil.

A bench test (Stirred Oxidation Test) for pre-evaluation of inhibition of sludge (naphtha insolubles) varnish and acidity formation by dispersant-detergent additive consists of dissolving 6 grams of the additive in 300 grams of solvent extracted SAE 30 weight oil in a beaker, suspending in the oil 5 square inches of copper and 10 square inches of iron as oxidation catalysts, maintaining the beaker and its contents at 330 F. (22 F.) while stirring with glass stirie the beakers contents in contact with air at 1300 r.p.m. Four glass varnish rods (6 mm. diameter) are inserted in the stirred oil. The varnish on the rods is evaluated on a scale of 0 to 10 where 10 is a clean rod. The naphtha insolubles (sludge) is measured as reported as weight percent and acidity is expressed in milligrams KOH per gram of sample. These values are determined at 24, 48 and 72 hour test durations. For such tests using high molecular weight Mannich condensation products of this invention, the results are tabulated below.

STIRRED OXIDATION TEST Example 8 There are combined, heated and stirred at 200 F., 0.182 mole of polypropyl-substituted phenol (800 Mn) and 0.031 mole tetraethylene pentamine. Then 0.182 mole formaldehyde is added as 14.7 ml. formalin (37% CH O) over a 45 minute period. Thereafter the temperature was increased to and held at 300 F. for four hours. Those amounts of phenol, amine and aldehyde reactants provided the respective molar ratio of 110.1721. By-product water is removed. The dried product is all high molecular weight Mannich condensation product (1677 fin) containing 1.61% oxygen and having a viscosity of 7733 SSU at 210 F. Such a product is soluble in lubricating oil, e.g., SAE SW, 10 and 30 weight oils, up to about 70 weight percent.

Example 9 There are combined, heated and stirred at 200 F., 800 grams of SAE 5W oil containing 68 weight percent (0.658 mole) polypropyl-substituted phenol of 830 fin and 62 ml. (0.329 mole) tetraethylene pentamine. Then 54 ml. formalin (37% CH O) to provide 0.658 mole formaldehyde is added at one time. As the reaction temperature increased extra heat is applied and nitrogen injection is started. Heating to and maintaining at 325-350 F. for 2.25 hours was practiced. The dried product (882.75 grams) is high molecular weight (1462 fin) Mannich condensation product in 256 grams of oil and has a viscosity of 3284.8 SSU at 210 F., a nitrogen content of 2.25%, an oxygen content of 1.57% and a specific gravity at 60 F. of 0.899. Those amounts of phenol, amine and aldehyde reactants provide the respective molar ratio of 1:0.5:1. This product is tested in a crankcase lubricant oil formulation in Lincoln Sequence V Engine Test hereinafter described. That crankcase lubricant oil formulation contains:

The sludge rating was 37.3 (50 is clean, no sludge), the varnish rating was 35.2 (50 is clean, no varnish) and oil ring plugging is 5%. Sludge and varnish ratings of 40 to 45 ranges can be achieved by increasing the concentrations of Example 9 product from 4 to 5 volume weight percent and also using 1.0 weight percent 300 total base numbermagnesium'salt of an alkylated benzene sulfonic acid.

Example 9 is illustrative of the conventional one-step preparation of the high molecular weight Mannich condensation product prepared from high molecular weight alkyl-substituted phenol, poly amine and formaldehyde used in the respective molar ratio of 2:1:2.

Example 10 The same reactants are used in the same amounts as in Example 9, but in the two-step condensation. 0.658 mole of the 827 Mn polypropyl phenol (68% in oil) and 0.329 mole of tetraethylene pentamine are combined, heated and stirred at 200 F. and to this stirred mixture 0.329 mole of formaldehyde is added. Then this product is heated at 300 F. to remove by-product water. When the dry first condensation product cooled to 200 C. flh'ere is added 0.329 mole additional formaldehyde. This second condensation product is heated to 330 F. and nitrogen is injected until the product is dry. The dried product will have physical and chemical properties substantially the same as those shown for Example 8 product and will have substantially the same in-service use function as a dispersant-detergent additive agent for lubricating oils.

A high molecular weight Mannich condensation product can be prepared from melamine as the source of NH containing reactant as illustrated by the following preparation.

13 Example 11 There are combined, stirred and heated to 200 F., 200 grams of a solution of (83%) polypropyl-substituted phenol (0.186 mole) of 892 Mb in SAE W weight oil and 7.8 grams (0.062 mole) of melamine. Then milliliters of formalin (37% CI-I O) to provide 0.186 mole formaldehyde is added and the mixture became milky white. The milky white appearance remained until the stirred mixture is heated to 470480 F. whereupon Water vapors came off and water condensate appeared in an air cooled vapor take-off condenser. The resulting product is heated at 370-380 F. until dry. The ratio of substituted phenol, amine and formaldehyde reactants are in the respective molar natio of 1:0.3321. The dried product is an oil solution of the high molecular weight Mannich condensation product of melamine. A carbon black suspension test (conducted as hereinbefore described) provided a stable carbon black suspension for 64 hours.

Example 12 -An oil solution of high molecular weight Mannich condensation is prepared from 2500 grams of the oil solution (45.9%) of 1600 Mn polybutyl-substituted phenol (0.716 mole), 0.334 mole of tetraethylene pentamine and 1.20 mole of formaldehyde to provide the reactants in the respective molar ratio of 1:0.466:1.675. The solution of polybutyl-substituted phenol, tetraethylene pentamine and 350 grams of SAE 5W oil are combined, stirred and heated to 150 F. The addition of formaldehyde (as formalin) caused the temperature to increase to 180. Thereafter nitrogen is injected into the stirred solution and it is heated to 300 F. and held at that temperature for three hours while by-product water is thus driven off. The dry oil solution has a viscosity of 1175 SSU at 210 F. and a nitrogen content of 0.72%. The clarity of the solution is excellent before and after filtration. Spot Dispersancy Test values (test herein described) were 67.3 and 81.6 for 0.5 and 2.0 weight percent high molecular weight Manm'ch condensation product use, respectively.

Example 13 An oil solution of 1654 Mn Mannich condensation prodnet is prepared from 1000 grams 1280 fin polypropyl phenol (0.64 mole) dissolved in SAE 5W oil as 77% solution, 0.64 mole formaldehyde (formalin), 0.32 mole tetraethylene pentamine :and diluent SAE 5W oil are heated to 300 F. for 3.5 hours. A small amount of a polysilicon anti-foam agent is used to suppress foaming. The resulting solution of this high molecular weight Mannich product is bright although dark in color and has an oxygen content of 1.60% and 1.74% nitrogen.

The following examples illustrate the preparation of the preferred high molecular weight bis-Mannich products of respective reactant molar ratio 1.0:0.7-1.0:1.52.1 using the before described two-staged condensation method of preparation.

Example 14 To prepare N-mono-C alkylbenzyl tetraethylene pentamine there is used an alkylphenol (mainly p-alkyl) of number average molecular weight (Mn) of 890 (average of 55 carbons in alkyl groups) obtained by alkylating phenol with a polypropylene having about 55 carbon atoms. The alkalation product contains 80 percent by weight of said 890 1\ .[n alkylphenol and 200 grams provides 0.18 mole of the 890 fin alkylphenol. A mixture of 200 grams (0.18 mole) 80% of 890 fin alkylphenol and 34 milliliters (0.18 mole) tetraethylenepentamine is stirred and heated to 210 F. and then 5.4 grams formalin (37% CH O) is added to provide 0.18 formaldehyde. The temperature of the reaction mixture increased to 300 F. Nitrogen at 1.5 (c.f.h.) cubic feet per hour (measured at 77 F. and atmospheric pressure) is injected into the resulting reaction mixture at 320 to 340 F. for five hours. The resulting product is a light colored liquid. By analysis this product contains 4.46% nitrogen, 2.50% oxygen and has a 210 F. viscosity of 2466 SSU (Saybolt Seconds Universal). This product contains the N-mono- C alkylphenol, formaldehyde and tetraethylene petamine in the mole ratio of 1:1:1, i.e., equimolecular proportions of the three reactants.

The above product is stirred and cooled to 200 F. and 5.4 grams formalin (37% CH O) providing 0.18 mole formaldehyde is added. Thereafter this mixture is stirred and heated to 340 F., held at 340 F. while injecting nitrogen at 1.5 c.f.h. for five hours. The resulting product is clear, dark and viscous. This product has a 210 F. viscosity of 14,515 SSU and by analysis has 3.14 weight percent oxygen and 4.14 weight percent nitrogen. The N-substituted amine product produced by the foregoing reaction is illustrated by substituting in structural Formula (I) and (II) C alkyl for each R and (HNC I-I for each (ANH) This compound has a number average molecular weight of about 2196 and has 5.1 percent by weight nitrogen. The resulting product has 40 grams diluent, mainly residue nonreactive polypropylene from the alkylation, and thus the 4.14 percent nitrogen by weight of the product corresponds to about that of 0.09 mole of the foregoing substituted amine product with the 40 grams diluent.

An amount of the product of Example 14 containing 0.5 gram of the disubstituted amine shown is added to a measured volume of crankcase lubricant oil formulation which had been used in a Lincoln Sequence V Engine Test for 384 hours (twice the time of the standard test time). To the same volume of used crankcase oil from the same 394 hour Lincoln Sequence V Engine Test there is added 0.5 gram N ,N -bis(polybutenylsuccinimide) of tetraethylene pentamine (bis-succinimide) whose polybutenyl group has a molecular weight of about 860. These two compositions are heated and stirred at 300 F. for 16 hours and an aliquot of each is transferred to blotting paper. A control is made at the same time by stirring and heating at 300 F. for 16 hours a third volume of used oil from the 394 hour Lincoln Sequence V Engine Test and depositing an aliquot on blotting paper. The remainder of each treated used crankcase oil (control-no addition agent) is permitted to stand and the time is measured for the substantially complete separation of oil from sludge. The deposits on the blotting paper are measured to obtain the average diameter of the outer oil ring (Do) and the average diameter of the inner sludge ring (Ds). The ratio of Ds/Do is an indication of the detergent-dispersant property of the addition agent. These ratios and the sludge settling tests are shown in Table I.

TABLE I (Used Lincoln Sequence V oil-394 hours The process of Example 14 is repeated by heating and stirring 1000 grams (0.9 mole) of 1110 Mn alkylphenol (alkyl group derived from polypropylene) and milliliters (0.9 mole) tetraethylene pentamine (TEPA) to 200 F. and then adding formalin to provide 0.90 mole formaldehyde. Thereafter this mixture is heated to 300 F. with nitrogen injection at 1.0 c.f.h., during nitrogen injection the temperature increased to 350 F. and held at this temperature for 10-15 minutes and then dropped to 320 F. at the end of 2 hours nitrogen injection. The resulting product, a clear liquid, is diluted with 1200 grams SAE 5 oil (40 weight percent of the 1:1:1 reaction product. The oil diluted product is cooled to 200 F. and 0.9 mole formaldehyde is added with stirring. This mixture is heated to 340 F. and held at 340 F. while injecting nitrogen at 1.0 c.f.h. for about 3 hours. The resulting product is filtered through celite at about 300 F. The resulting filtrate is a light colored, crystal clear product. The filtrate at 210 F. has a viscosity of 147.7 SSU and is found to contain 2.25 percent nitrogen and 1.66 percent oxygen, both by weight. The substituted amine prod not is a 1 mole alkylphenol:1 mole TEPA 2 moles formaldehyde compound.

Example 16 The method of Example 14 is repeated using a 47% by weight solution of Mn 900 alkylphenol (alkyl is from polypropylene) in SAE 5 oil to provide 0.85 mole of alkylphenol, 0.85 mole TEPA and two (69 ml.) portions of formalin (37% CI-I O) to provide 0.85 mole formaldehyde at each addition. The resulting filtered product is a dark, bright and clear liquid having viscosities of 352 SSU at 210 F. and 12,677 SSU at 100 F. By analysis this liquid product is found to contain on a weight basis 2.88% nitrogen, 1.2% oxygen, and 52% of the substituted amine product (like the structure depicted in Example 14) from the 1 mole Mn 900 alkylphenol:1 mole TEPA:2 moles formaldehyde reactant mole ratio.

Example 17 There are combined 100 grams 2220 Fin alkylphenol (0.045 mole), 100 grams SAE 5 oil and 0.045 mole TEPA. This mixture is stirred and heated to 187 F. and 0.045 mole formaldehyde is added. This liquid mixture is stirred and heated to 320-340 F. and nitrogen is injected at 1 c.f.h. for 2 hours. Thereafter the liquid mixture is stirred and cooled to 200 F., a second addition of 0.045 mole formaldehyde is made and then the liquid mixture is stirred and heated again at 320340 F. with nitrogen injection at 1 c.f.h. for about 3 hours. The resulting liquid is filtered at about 300 F. through celite. The filtrate is light in color, bright and clear liquid having a 210 F. viscosity of 2720 SSU. By analysis this product contains on a weight basis 0.85% nitrogen, 0.82% oxygen and about 40% of the 1 mole 2200 M11 alkylphenol:1 mole TEPA:2 moles CH O mole ratio substituted amine product.

Example 18 There are combined, stirred and heated to 180 F., a solvent extracted SAE 5W oil solution containing 2.38 millimoles of alkylphenol obtained by alkylating phenol with a 70,000 Mn polybutene (solution has a 100 F. viscosity of 38,880 SSU) and 2.38 millimoles TEPA. Then two additions of 2.38 millimoles formaldehyde are made at 140 F. and 160 F., respectively, with heating to 300' 320 F. and 1 c.f.h. nitrogen injection after each formaldehyde addition. By this method a very high molecular weight substituted amine product of 1 mole alkylphenol:1 mole TEPA:2 moles formaldehyde.

Example 19 There are combined, stirred and heated to 160 F. 820 grams of 1800 Mn alkylphenol (alkyl group derived from polybutene) providing 0.365 mole of said alkylphenol, 820 grams solvent extracted SAE 5W oil and 0.365 mole TEPA. Then 0.365 mole formaldehyde is added, the reaction mixture is stirred and heated to 320 F., held at 320 F. for 90 minutes and nitrogen is injected at 1.5 c.f.h. at 260 F. for one hour. The liquid mixture is stirred and cooled to 180 F. and a second 0.365 mole formaldehyde addition is made, the resulting liquid reaction mixture is stirred and heated to 320 F., held at 320 F. for 90 minutes and nitrogen at 1 c.f.h. is again injected at 260 F. This liquid is filtered through celite at about 260 F. The 210 F. viscosity of the filtrate is 687 SSU, and, by analysis, is found to contain 0.531% oxygen, 1.4%

nitrogen, a total base number (TBN) of 30.61 and contain 42.5% of the 1 mole of 1800 Mn alkylphenol:1 mole TEPA:2 moles formaldehyde mole ratio substituted amine.

Example 20 There are combined, stirred and heated to 170 F. 700 grams solvent extracted SAE 5 oil, 0.284 mole TEPA and 966 grams of 2358 fin alkylphenol (alkyl group from polybutene) providing 0.284 mole of said alkylphenol. Then 0.284 mole of formaldehyde is added, the mixture heated to 320340 F. and held at 320'-340 F. for 2 hours while injecting nitrogen at 2.0 c.f.h. An additional 0.284 mole of formaldehyde is added to the liquid cooled to 180 F. and this liquid mixture is heated to 340 F., held at 340 F. for 2 hours while injecting nitrogen at 2 c.f.h. The liquid product is filtered. The filtrate has a 210 F. viscosity of 1191 SSU and is found to contain 1.13 percent nitrogen by weight. In this manner there is produced a solvent extracted SAE 5W oil solution of the 1 mole 2358 Mn alkylphenol:1 mole TEPA:2 moles formaldehyde mole ratio substituted amine.

Example 21 The process of Example 20 is repeated using 0.31 mole each of TEPA and 1937 Mn polybutylphenol (polybutyl group has average of 131 carbons) as a 34 weight percent solution in SAE 5 oil. Two 0.31 mole CHgO portions are added at 180 F. with heating to 320 F. and nitrogen injection for 40 minutes after first addition and 150 minutes after second addition. The filtrate is a clear, bright liquid of light color having a 210 F. viscosity of 931 SSU, a 26.44 TBN and containing 1.2 percent nitrogen by weight. The product solute is of the mole ratio of reactants of 1 mole C alkylphenol:1 mole TEPA:2 moles CH O.

Example 22 In this preparation, bis-carbamate of TEPA, i.e. the compound derived by reacting 2 moles TEPA with one mole urea to split out two moles ammonia is employed in place of TEPA. There is employed 0.031 mole of said bis-carbamide of TEPA, 0.031 mole of 1713 fin polybutylphenol dissolved in SAE 5W oil (143 grams of solution) and two 0.031 mole portions of CH O each added at 180 F. with heating to 320 F. for minutes and 1.5 c.f.h. nitrogen injection after each addition. The resulting liquid product is filtered. The filtrate is a solution of the 1 mole-polybutylphenolzl mole bis-carbamide of TEPA:2 moles CH O substituted amine wherein the polybutyl substituent has an average of carbons.

The use of bis-carbamide of polyalkylene polyamines, i.e. having the generic formula where x and A are the integer and divalent alkylene hydrocarbon hereinbefore defined, in place of the polyalkylene polyamine is a convenient means for introducing nearly the same number of nitrogens into the product of 1 mole 0 alkylphenol:1 mole polyalkylene polyamine: 2 mole CH O by the use of a lower nitrogen lower molecular weight polyalkylene polyamine starting material in place of a higher molecular weight polyalkylene polyamine. In fact said bis-carbamides are useful replacements for TEPA. Also by the use of said bis-thiocarbamides wherein sulfur replaces oxygen in the generic formula hereinbefore shown, the sulfur provides extreme pressure lubricant properties to the detergent-dispersant 081 1210911 inhibiting compounds of this invention.

Example 23 light and clear liquid has a 210 F. viscosity of 1531 SSU, a specific gravity of 0.08996 at 77 F. and from analysis is found to contain 0.67% nitrogen by weight.

By substituting 0.058 mole bis-carbamide derived from D-ETA in the foregoing reaction, a liquid product of 1.3 to 1.5% nitrogen by weight may be obtained.

As an example of such a sulfur-containing dispersantdetergent oxidation inhibiting compound of this invention, there are reacted 0.32 mole of thiourea and 0.64 mole of diethylene traimine to produce 0.32 mole bis-thiocarbamide of diethylene triamine:

(H2NC zH NH-C 2H4) NH-fiNH-( C 2H4-NH-C 2H4-NH2) Example 26 under conditions splitting out two moles ammonia. Then There are eembilled, Stirred and heated to 0.32 mole of this bis-thiocarbamide is combined with 0-477 mole DETA and 2500 grams of a Solution of 1088 grams of 1836 En C alkyl-substituted phenol to 2000 MR p y y p mole) in SAE 5W provide 0.32 mole of C alkylphenol. After stirring and A first addition of 0.475 mole formaldehyde is made and heating this mixture to 140 F. there is added 0.32 mole the mixture is stirred and heated to 220 F. The second formaldehyde, this mixture is heated to 340 F., held at addition of 0.475 mole formaldehyde is about 45 minutes 340 F. while injecting 2.2 CFH nitrogen for 75-80 later at 220 F., i.e. the reaction mixture is not cooled. minutes, cooled to 200 R, an additional 0.32 mole The resulting liquid reaction mixture is then stirred and CHzO is added, and the resulting liquid is stirred and heated to 300 F., held at 300 F. for 2 hours and filtered heated to 340 F. and nitrogen at 2.2 c.f.h. is injected at about 300 F. The filtrate, a light clear liquid has a at 340 F. for 2 hours. The resulting mixture is filtered. Viscosity of 1418 a specific g y of 0.

The detergency-dispersancy activity of the products at 77 F. and, by analysi has a nitrogen y of Examples 22 and 23 exceeds that of corresponding weight.

products prepared from TEPA or diethylene triamine Example 27 (DETA) by more than the mere difference in nitrogen atom content might suggest. There are combined, stirred and heated to 140 F., a

Example 24 solution (2500 grams) containing 38% of 1713 En alkylphenol (0.482 mole) in SAE 5W oil and 0.482 TEPA.

Three Preparatlons of 1 mole 50+ alkylphenolil mole The first addition of 0.482 mole formaldehyde is made, TEPA=2 moles formaldehyde p are carried out the reaction mixture is stirred and heated to 300 F. using 37 Weight PefeeIlt 1937 M11 p y p 3 with nitrogen injection at 1.5 c.f.h. for 60 minutes, cooled weight percent 1713 fin polybutylphenol and weight to 160 F. for the second addition of 0.482 mole formaldepercent 1937 Mn polybutylphenol each in SAE 5W oil as y and then Stirred and heated again to with source of the C alkylphenol reactant. These preparanitrogen injection at 1.5 c.f.h. and reacted for 60 minutes. tions are hereinafter identified as 24A, 24B and 24C, The liquid reaction mixture, SAE 5W oil solution of respectively. The sequence of steps, conditions and 5 reaction product, has a 210 F. viscosity of 766 SSU amounts of reactants is set forth in Table II for these and is found by analysis to have 1.25% nitrogen and a three preparations. 31.4 TBN.

TABLE II Process steps 24A 24B 24C (1) Combine, stir and heat 0.35 mole each TEPA and alkyl- 0.54 mole each TEPA and alkyl- 0.45 mole each alkylphenol and phenol. phenol. TE]? (2) Add CHQO 0.35 mole at 160 F 0.54 mole at 160 F 0.45 mole at 160 F. (3% lietat to 320 F. and hold with N: 1.5 hour, 1.5 c.f.h. N2 1.5 hour, 1.5 c.f.h. N2. 1.5 hour, 1.5 c.t.h. N1.

mec 1011. (4) Cool and add CHzO 0.35 mole at 180 F 0.54 mole at 180 F 0.45 mole at 180 F. (5) Repeat Step (3) 1.5 hour and 1.5 c.f.h. N2 1.5 hour and 1.5 c.f.h. N2-- 1.5 hour and 1.5 c.f.h. N1. (6) Filter At 300 F At 300 F At 300 F.

Small samples of 24A, 24B and 24C filtrates are taken The screening detergentdispersant test using crankand the remainder of 24A, 24B and 24C are combined case drain oil from a Lincoln Sequence V engine test and stirred. This mixture is hereinafter referred to as hereinbefore described is carried out with some of the Example 24 Composite Product and is found to have products of the Examples of 13 through 27. There is a 210 F. viscosity of 780SSU and a 29.88 TBN. shown in Table III the product used identified by Ex- EX am P16 25 ample number, the amount of reaction product in grams (not grams of solution produced) and the ratio of Ds There are combined, stirred and heated to 140 F. (average diameter of sludge ring) and Do (average 0.058 mole diethylene triamine and 306 grams of a diameter of oil ring) 100.

TABLE IIL-RING RATIO DETERGENT-DISPERSANT SCREENING TEST Example ":1 Control 4 16 17 19 22 4 24 24A. 26 21 Grams None 0.5 0.4 0.5 0.5 0.28 0.25 0.25 0.5 0.28 0.5 0.56 Ds/DoXlOO 50 92.5 s7 s9 97 77.5 71.5 79.4 90 84.3 88.4 93.8

1 Composite of Example 24.

38% l ti f 2000 M}; polybutyl henol 1058 l The same test procedure conducted with 2:1:2 mole in white oil. A first addition of 0.058 mole formaldehyde ratio of 83 Mn l y p 1140 Mn alkylphenol have is made and the mixture is stirred and heated to 220 DO/DSX 100 at s f 7 and 7 respectively at use of F. and held at 220 F. for minutes. Thereafter the g These made from 2 moles of alkylphenol mixture is cooled to 200 F. and the second addition of g 2 10 20 carbons in the alkyl Substitllent Such as 1 mole 0.05 8 mole formaldehyde is made. This mixture is stirred nonylphenolil mole TEPA and 2 1110168 f rm ld hy e (10 and heated to 300 F. and held at that temperature for not have a sufliciently Oil so yl ('R group) sub- 2 hours. There is no evidence of unreacted formaldehyde stituent on the ring of the hydroxy benzyl group of the or amine. The liquid product is filtered. The filtrate, a diand poly(hydroxyalkyl benzyl) amines to disperse There are combined, stirred and heated to 160 F., 2000 grams of SAE 5 oil solution of (45.9%) polybutylsubstituted phenol of 1600 En to provide 0.716 mole of that substituted phenol, 94 grams (0.495 mole) tetraethylene pentarnine and 420 grams of SAE 5W oil. Then one drop of liquid silicon anti-foam agent and 100 milliliters of formalin (37% (EH to provide 1.318 moles formaldehyde are added at one time to the hot stirred mixture. After the temperature increase from the reaction of the added formaldehyde has occurred, the temperature of the stirred solution of reaction product is increased to 300 F. and nitrogen is injected into the stirred and heated solution. Nitrogen injection and stirring is continued while the solution is held at a temperature of about 310 F. (:10 F.) for two hours to drive 01f by-product water. Then the solution is filtered. The hot filtrate is bright, i.e., has a good clarity. The solution contains about 42% by weight of high molecular weight Mannich condensation product, a nitrogen content of 1.02% and a viscosity of 1002.5 SSU at 210 F. The reactants polybutyl-substituted phenol, amine and formaldehyde are used in the respective molar ratio of 1:069: 1.835.

The product of the foregoing example, oil solution used with Lincoln Sequence V oil test (0.6% solute of Example 28), before described, gave a Ds/Do ratio of 91 which is indicative of super dispersant-detergent properties of the high molecular weight Mannich product.

ENGINE TESTS The effectiveness of the substituted amine products of this invention as detergent-dispersant addition agent for lubricant oil compositions can be demonstrated by their use in such compositions as crankcase lubricants in actual engine tests such as the Lincoln Sequence V Engine Test, the .Ford 289 Engine Test and the L-38 Engine Test aforementioned.

It will be noted that the hydroxyalkyl benzyl substituted amine products of this invention used in said tests unlike hydroxyalkyl benzyl substituted amines of the prior art are not used as their calcium, barium, magnesium or other alkaline earth metal or alkali metal salts.

The compounds of this invention can function as detergent-dispersant addition agents in lubricant oil compositions in the weight percent range suitably of from 0.1 to 10%, desirably in the range of 0.2 to 8.0% and preferably in the range of 0.5 to 5%. However, lubricant oil solutions having to 50% or more by weight of the novel hydroxyalkyl benzyl substituted polyalkylene amines of this invention including the bis(polyalkylene amine) carbamides and thiocarbamides are useful in the preparation of finished lubricant oil compositions because they can be readily and conveniently combined with concentrates of other lubricant oil addition agents such as oil solutions of the alkaline earth metal sulfonates, e.g. normal and high based calcium and magnesium salts of petroleum sulfonic acids such as sour oil, mahagony acid and alkyl substituted benzene sulfonic acids having alkyl hydrocarbon groups of a carbon content of greater than 16 and more specifically of 30 to 29,000 carbon atom alkyl hydrocarbon group size, oil solutions of zine dialkyldithiophosphates and other concentrate solutions of lubricant addition agents all of which are used for their antiwear, anti-corrosion, anti-foam, oxidation inhibition, oiliness, viscosity-index improving properties. For example, the oil solution concentrates having 10 to 50% by weight of the novel substituted amine products of this invention can be easily blend mixed with base oils and oil solution concentrates of the aforementioned addition agents having anti-wear, anti-corrosion, viscosity-index improving, antifoam, etc. properties in transfer line blending, i.e. each concentrate and base oil are gharged to a transfer ling from sources of supply of each concentrate in the required proportions so that there flows from the transfer line a completely finished, fully formulated lubricant oil composition ready for packaging in quart, gallon, 5 quart, 30 gallon or 55 gallon containers or tank car and/or truck for delivery to the ultimate consumer. Such finished and fully formulated lubricant oil compositions are useful as crankcase lubricants for automobile, truck and railway gasoline and/or diesel engines.

The aforementioned Lincoln Sequence V Engine Test, Ford 289 Engine Test and L-38 Engine Test are conducted in the following manner.

LINCOLN SEQUENCE V ENGINE TEST Phase 1 Phase 2 Phase 3 Duration 45 minutes" 2 hr 75 minutes Speed, r.p. 2,500 2,50 Load, lbs No load HP)....... (105 HP). Temperature, F.:

Water out.- -120 -130 -175. Oil sump 120-125. -180 205-210. /F 9.5:l:0.5 15.5:|:0.5 15.5=l;0.5.

The four-hour cycle is reset at total of 48 times (192 hours running time). After each 16 hours of operation the engine is shut down for 8 hours. Two-ounce samples of oil are taken every 30 hours and the oil level is adjusted with fresh oil to a level of five quarts. Added oil is weighed. At the time of the test, the hot oil is drained, weighed and recorded. The engine is then disassembled and tested for deposits of varnish and sludge among other observable results as set out in the table below. Engine components are examined visually and rated on a scale of 1 to 10, 10 being a perfect reading indicating no sludge or varnish. A rating of 50 for total sludge and for total varnish is considered perfect; a rating of 60 percent or lower is considered passing for screen clogging; and a rating of 50 percent or lower is considered passing for ring plugging.

=FORD289 ENGINE TEST The Ford 289 cubic inch displacement engine test, hereinafter designated as F-289 Test, is conducted in the same manner as the Lincoln Test Sequence V except for the apparent difference in test engines. This F-289 Test is more severe with respect to both sludge and varnish formation and deposition. Also the E289 Test is conducted with vapors from the crankcase being introduced into the engine fuel intake system by means of a positive crankcase ventilation system which, in part, results in the more severe sludge and varnish formation during test operation.

L-38 ENGINE TEST The L-38 Engine Test is also known as CLR L-38 Engine Tes and is designed to evaluate high temperature oxidation stability of the formulated lubricant oil and such evaluation is based on piston varnish deposit and copper-lead bearing corrosion. In this test a single cylinder Water cooled Labeco oil test engine is operated at 3150 rpm. for 40 hours with the test oil formulation. The oil is maintained at 300 F. and cooling water is maintained at 195 F. Copper-lead connecting rod bearings are weighed before and after the 40 hour test. Bearing weight loss (BWL) of 50 milligrams or less is desired. After the 40 hour test the piston is visually evaluated and a varnish value is assigned by comparison to varnish deposit pictorial standards having assigned values of 1 to 10 for the color and extent of varnish deposit. In this varnish value scale of l to 10 the value 10 represents a clean and varnish free piston and the value 1 represents a substantially complete dark varnish coated piston. To qualify as a preminurn oil additive the varnish value should be 9.0 and above.

The following lubricant formulations in which all 5 percent of the addition agent indicated are by volume, are prepared for use in the foregoing engine tests. Products of this invention are identified by reference to the appropriate example of preparation and the volume percent solution produced. The weight percent of the solute product or dissolved is that of the active ingredient, i.e. the dissolved substituted amine product, is shown under weight percent. Where used Ca-300 and Mg-300" designate the respective sulfonates dissolved as concentrates in SAE 5W oil with a total base number of 300 for the solution and other higher or lower numbers designate higher or lower solution total base numbers. The designation ZOP is used to identify a zinc dialkyldithiophosphate anti-wear-anti-corrosion addition agent whose alkyl groups are derived from the conjoint reaction of three different alcohols, two of which are primary alcohols such as C and C oxo-derived alcohols and the third is a secondary alcohol such as isopropyl or isobutyl alcohols, with dithiophosphoric acid and the total moles of the three alcohols is the stoichiometric amount required to obtain dialkyl dithiophosphoric acid for reaction with zinc or zinc oxide. Thus the Z01 is a statistical mixture of the zinc salts having the three aforementioned alcohol derived alkyl groups. Since the relative proportions of iso, C primary and C primary alcohols can be varied considerably to provide an oil-soluble zinc salt, their precise proportions need not be indicated. A ZOP product typical of that used is a concentrate zinc dialkyl dithiophosphate in SAE W oil having the following typical properties: Solution has 210 F. viscosity of 67 SSU, 5% Zn, 8% P and 16% S, all by weight.

Percent Formulation Vol. Wt. Ca- Mg- Base No. No. percent percent ZOP 300 300 oil The results of using above formulations in the Lincoln Sequence V Engine Test are presented in Table V.

TABLE V.LINCOLN SEQUENCE V ENGINE TEST RESULTS The results of the use of the indicated formulations in the Ford-289 Engine Test are given in Table VI.

TABLE VI.-FORD-289 ENGINE TEST RESULTS Percent 011 ring Formulation No; Sludge Vamlsh plugging TABLE VIL-CLR L-38 ENGINE TEST RESULTS Piston Bearing wt.

Formulation varnish loss, mg.

11 9. 5 32 VII 9. 5 57 Lubricant oil formulations prepared from other of the products of this invention when used in the foregoing engine tests in the same or higher amounts of active ingredient will provide for the obtention of the same or superior results.

In general, the active ingredient product of this invention obtained as solute in light mineral oil have structural formulae as hereinbefore shown.

What is claimed is:

1. An improved lubricating oil comprising said lubricating oil and 0.05 to 25% by weight of said lubricating oil of a condensation product of (1) high molecular weight alkyl-substituted phenol wherein said alkyl substituent has a molecular weight in the range of 700 to 280,000, (2) a polyalkylene polyamine of the formulae:

wherein x is an integer from 1 to 10, A is a divalent saturated hydrocarbon group having 2 to 8 carbon atoms and Z is oxygen or sulfur; and (3) an aldehyde wherein the respective molar ratio of reactants is 1:0.110:1-l0.

2. The improved lubricating oil composition of claim 1 wherein the alkyl-substituent has a molecular weight of 800 to 2500.

3. The lubricating oil of claim 1 wherein the aldehyde is selected from the group consisting of formaldehyde and paraformaldehyde.

4. The lubricating oil composition of claim 1 wherein the amine reactant has the formula H N-A -N-CN A-N H t I H H H H x wherein x is an integer from 1 to 10, A is a divalent saturated hydrocarbon group having 2 to 8 carbon atoms and Z is oxygen or sulfur.

5. The lubricating oil of claim 1 wherein the alkylsubstituent has an average molecular weight in the range of 800-2500, the polyalkylene polyamine has the formula 31- (liq-C 11 H xNHB wherein x is an integer from 1 to 10, the aldehyde is formaldehyde, and the respective molar ratio of reactants is 1.0:O.7-l.0:1.5-2.1.

6. The lubricating oil of claim 5 wherein the polyalkylene polyamine is tetraethylene pentamine.

No references cited.

DANIEL E. WYMAN, Primary Examiner W. I. SHINE, Assistant Examiner Column 7,

4 Column;

Patent No. I i I 3,79 5

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